用于甲苯歧化与C9芳烃烷基转移过程先进控制的反应动力学模型

针对某实际工业装置，建立了甲苯歧化和C₉芳烃烷基转移反应简化机理模型，用于反应过程的监控、优化及大型轴向流反应器内各物料组成分布的预测；采用四-五阶Runge-Kutta法对模型方程进行了数值求解，并基于多套稳态平衡数据，采用Broyden-Fletcher-Goldfarb-Shanno(BFGS)优化算法对动力学模型参数进行了估计；针对不同的进料组成和操作条件，对工业装置进行模拟仿真。结果表明，模型估计值与工业标定值相当吻合，达到了工业应用的模拟精度要求。所建立的模型形式简单、参数估计方便，适用于工业装置的离线仿真和在线软测量。     

苯乙烯连续搅拌釜式本体聚合工业过程模拟

采用了机理分析建模法对苯乙烯工业本体预聚过程进行了模型化研究，并通过对流体在反应器中混合模式的分析，表明预聚釜可视作全混流（CSRT）反应器模型，此外对热聚合机理中的引发级数和终止反应进行了考察，利用预聚釜的工业数据确立了三分子引发，同时考虑偶合和歧化终止以及向溶剂链转移的反应机理模型，并选取了合适的动力学参数，然后利用工业装置采集的数据进行了模拟，从宏观转化率，平均分子量和微观分子量分布两个方面对模型进行了验证，模拟结果和工业数据符合得较好，该模型方程不仅能模拟稳态，非稳态预聚过程，同时也为装置开发新产品，改造扩建，优化操作方案等提供了理论基础。     

乙炔法气相合成醋酸乙烯工业固定床反应器的优化操作的…

在前面乙炔法气相合成醋酸乙烯的宏观动力与失活动力学研究的基础上，建立了工业固定床反应器的数学模型，同时为优化操作计算机模拟提供了一系列计算机软件。依据工厂试生产数据用该模型进行了计算机模拟，得到了工业固定床反应器的反应动力学和失活动力学模型参数。     

乙炔法气相合成醋酸乙烯工业固定床反应器的优化操作的研究Ⅲ工业固定床的数学模型与操作优化的计算机模拟

在前面乙炔法气相合成醋酸乙烯的宏观动力学与失活动力学研究的基础上，建立了工业固定床反应器的数学模型，同时为优化操作计算机模拟提供了一系列计算机软件。依据工厂试生产数据用该模型进行了计算机模拟，得到了工业固定床反应器的反应动力学和失活动力学模型参数。基于该模型对工业操作进行优化模拟计算［１～４］，生产试验的结果表明，按照计算机所选择的适当的操作条件和升温制度，可在保证日产率的前提下延长催化剂使用周期     

尼龙66连续缩聚过程模拟

为加深对聚己二酰己二胺(尼龙66)缩聚过程的理解,指导尼龙66生产过程的优化和新工艺开发,本研究基于聚合反应特性以及反应器流体力学特征,耦合聚合反应动力学模型、水-聚合物体系的汽液平衡模型以及传质模型,建立了尼龙66连续缩聚过程管式反应器和后缩聚反应器的数学模型,实现了尼龙66连续聚合过程的模拟。聚合物分子量及水含量的模拟值符合工业生产数据,验证了模型的可靠性,模拟分析了聚合工艺参数对聚合物分子量及水含量的影响,结果表明减少醋酸含量、提高反应器温度、降低管式反应器和后缩聚反应器压力均有利于快速提升聚合物分子量。较优的工艺条件为后缩聚器温度280~285℃,卧管式反应器压力1.600~1.750MPa。建立的模型准确性好,可用于考察工艺参数的影响,指导工业应用。     

对苯二甲酸加氢精制反应器的数学模拟

分析了对苯二甲酸加氢精制固定床反应器的传质特性,在对反应器进行合理简化后,建立了对苯二甲酸加氢精制反应器的非均相一维平推流数学模型,对有关物性数据和模型参数进行了计算.利用该数学模型对工业装置对苯二甲酸加氢精制反应器进行了模拟计算,计算了各组分沿反应器床层的浓度分布.模拟结果与实验数据相吻合,说明建立的数学模型是可信的.     

乙烯氧氯化流化床反应器的模型化及操作条件优化

对工业乙烯氧氯化挡板流化床反应器建立了以两相理论为基础的多釜串联反应器模型,利用大量工业数据求解模型参数并检验模型,计算结果表明模拟值与工业值基本吻合.在此基础上,对反应器操作条件进行优化,得到不同生产负荷下的最优操作条件.     

甲缩醛氧化制甲醛固定床反应器的数学模拟

依据甲缩醛氧化制甲醛的宏观动力学模型和固定床拟均相二维模型，采用正交配置法模拟固定床单管反应器，模拟结果与试验数据基本一致，表明该反应器数学模型具有一定的可靠性和实用性。用此模型进一步考察了主要操作条件，催化剂稀释比和床展稀释长度对甲醛收率和热点温度的影响，为该过程的工业放大和反应器设计提供了依据。     

PX氧化反应器-结晶器串联过程的数学模型

在对二甲苯（PX）氧化反应器研究的基础上，建立了考虑结晶器中的反应、蒸发、杂质扩散等过程的反应器-结晶器串联的数学模型。模拟表明，该模型计算结果与工业实测数据吻合。串联操作在催化剂用量、燃烧消耗、产品收率等方面均优于单一反应器；通过提高结晶器温度。强化结晶器氧化作用，并调整氧化反应器和结晶器的负荷分配，可以达到增产效果。     

外循环喷雾式乙氧基化反应器的数学模型与模拟

对半间歇操作外循环喷雾式乙氧基化反应器的数学模型与模拟进行了研究,分析了反应器的特性,建立了同时考虑气液传质、动力学、汽液平衡、反应体积变化和惰性气氮气影响的反应器的数学模型和数值模拟算法。以合成聚乙二醇为例,模拟得到反应器中温度、压力、环氧乙烷浓度及乙氧基化产物随时间和空间位置的分布。模拟结果同工业操作数据进行了比较,结果表明了模型的可靠性。     

Investigation of the liquid recycle in the reactor cascade of an industrial scale ebullated bed hydrocracking unit

One of the commercial means to convert heavy oil residue is hydrocracking in an ebullated bed. The ebullated bed reactor includes a complex gas–liquid–solid backmixed system which attracts the attention of many scientists and research groups. This work is aimed at the calculation of the internal recycle flow rate and understanding its effect on other parameters of the ebullated bed. Measured data were collected from an industrial scale residual hydrocracking unit consisting of a cascade of three ebullated bed reactors. A simplified block model of the ebullated bed reactors was created in Aspen Plus and fed with measured data. For reaction yield calculation, a lumped kinetic model was used. The model was verified by comparing experimental and calculated distillation curves as well as the calculated and measured reactor inlet temperature. Influence of the feed rate on the recycle ratio(recycle to feed flow rate) was estimated. A relation between the recycle flow rate, pump pressure difference and catalyst inventory has been identified. The recycle ratio also affects the temperature gradient along the reactor cascade. Influence of the recycle ratio on the temperature gradient decreased with the cascade member order.     

接种污泥预处理对生物制氢反应器启动的影响

采用3个相同的EGSB反应器,以糖蜜废水为底物,分别对取自污水处理车间集泥井的缺氧污泥进行曝气预处理和加热预处理,通过与不经任何预处理的接种污泥（对照反应器）的启动试验进行对比,在其他启动控制条件相同的情况下,研究了接种污泥不同预处理对EGSB生物制氢反应器启动的影响。结果表明,与对照反应器相比,经过适当预处理的活性污泥接种至生物制氢反应器有利于反应器的高效快速启动,产氢微生物得到了有效的富集,在启动末期反应器各项指标均优于对照反应器。启动末期,接种污泥经过适当预处理的反应器,酸化率较未经预处理的反应器提高了10%~30%;产氢量提高了1.69~1.82倍。考虑到降低生物制氢的工业化应用成本及提高系统可操作性,本研究推荐应用曝气预处理方法对生物制氢反应器的接种污泥进行预处理,以获得其高效快速启动。     

丙烯氯醇化反应器操作优化

以１０,０００吨／年环氧丙烷装置氯醇化反应工段为对象,采用简化的机理模型,通过两相法实施过程的操作优化,考察了操作变量对反应过程的影响,并比较了不同优化目标对优化效果的影响,通过优化显著地提高过程的运行效益,并提出了进一步提高生产能力和优化效果的途径。     

Comparison of performance of an industrial VGO-treater with reactor model predictions

A simplified reactor model can be used for predicting the performance of an industrial VGO-treater. Laboratory-scale experiments performed on the same feed and catalyst as those in the industrial unit lead to a reactor simulation which agrees well with the data from this unit. In the laboratory experiments, it is possible to overcome the specific hydrodynamic problems of tricklebed reactors by appllying the catalyst dilution technique. Results obtained by this technique allowed the development of a reactor model which enables the user to simulate the adiabatic behaviour of the industrial reactor. In this way, the significant gap between the reaction temperature in the isothermal laboratory reactor and the WABT of the industrial adiabatic reactor can be bridged.     

Novel Gas-Liquid-Solid Reactors

Multiphase reactors involving gas, liquid, and solid phases have several important applications in the chemical industry, particularly in catalytic processes. Some of the well-known examples are: hydrogenation and oxidation of organic compounds, hydro-processing coal-derived and petroleum oils, Fischer-Tropsch synthesis, and methanation reactions. Due to the presence of three phases, the problem of reactor design is often important to achieve effective mass and heat transfer as well as a mixing pattern favorable to the particular process. The reactors are mainly of two types: (a) solid catalyst is suspended either by mechanical agitation or gas-induced agitation and (b) solid catalyst is in a fixed bed with concurrent or countercurrent feed of gas and liquid re-actants. The reactor types conventionally used in industry are: (a) mechanically agitated or bubble column slurry reactors and (b) trickle-bed or packed-bed bubble reactor. The various design and modeling aspects of these reactors have been reviewed by Satterfield [1], Chaudhari and Ramachandran [2], Shah [3,4], Ramachandran and Chaudhari [5], Shah et al. [6], and Herskowitz and Smith [7]. In several industrial processes these reactor designs are modified to achieve a certain specific objective, such as better heat or mass transfer, higher catalyst efficiency, better reactor performance and selectivity, etc. Similarly, specially designed reactors are often used for laboratory kinetic studies or to understand a certain phenomenon. Thus, novel multiphase reactors are becoming important from both academic and industrial viewpoints. Some of the recently introduced novel gas-liquid-solid reactor types are: (a) loop recycle slurry reactors, (b) basket-type reactors, (c) ebullated-bed reactors, (d) internal or external recycle reactors, (e) multistage slurry or packed-bed reactors, (f) column reactors with sieve trays or multiple agitators, (g) gas-induced agitated reactors, and (h) horizontal-packed-bed reactors. are being used in several new commercial processes, and various design aspects, such as hydrodynamics and mass and heat transfer, have been the subject of investigations in the last few years. However, no attempt to review the scattered information on these novel gas-liquid-solid reactors has been made. Therefore, the main objective of this paper is to review important developments in novel gas-liquid-solid reactors. For each type of reactor, advantages, disadvantages, and applications are discussed. Further, the status of information on hydrodynamics and mass transfer parameters and scale-up considerations is reviewed. These novel reactor designs are being used in several new commercial processes, and various design aspects, such as hydrodynamics and mass and heat transfer, have been the subject of investigations in the last few years. However, no attempt to review the scattered information on these novel gas-liquid-solid reactors has been made. Therefore, the main objective of this paper is to review important developments in novel gas-liquid-solid reactors. For each type of reactor, advantages, disadvantages, and applications are discussed. Further, the status of information on hydrodynamics and mass transfer parameters and scale-up considerations is reviewed.     

Novel Gas-Liquid-Solid Reactors

Multiphase reactors involving gas, liquid, and solid phases have several important applications in the chemical industry, particularly in catalytic processes. Some of the well-known examples are: hydrogenation and oxidation of organic compounds, hydro-processing coal-derived and petroleum oils, Fischer-Tropsch synthesis, and methanation reactions. Due to the presence of three phases, the problem of reactor design is often important to achieve effective mass and heat transfer as well as a mixing pattern favorable to the particular process. The reactors are mainly of two types: (a) solid catalyst is suspended either by mechanical agitation or gas-induced agitation and (b) solid catalyst is in a fixed bed with concurrent or countercurrent feed of gas and liquid re-actants. The reactor types conventionally used in industry are: (a) mechanically agitated or bubble column slurry reactors and (b) trickle-bed or packed-bed bubble reactor. The various design and modeling aspects of these reactors have been reviewed by Satterfield [1], Chaudhari and Ramachandran [2], Shah [3,4], Ramachandran and Chaudhari [5], Shah et al. [6], and Herskowitz and Smith [7]. In several industrial processes these reactor designs are modified to achieve a certain specific objective, such as better heat or mass transfer, higher catalyst efficiency, better reactor performance and selectivity, etc. Similarly, specially designed reactors are often used for laboratory kinetic studies or to understand a certain phenomenon. Thus, novel multiphase reactors are becoming important from both academic and industrial viewpoints. Some of the recently introduced novel gas-liquid-solid reactor types are: (a) loop recycle slurry reactors, (b) basket-type reactors, (c) ebullated-bed reactors, (d) internal or external recycle reactors, (e) multistage slurry or packed-bed reactors, (f) column reactors with sieve trays or multiple agitators, (g) gas-induced agitated reactors, and (h) horizontal-packed-bed reactors. are being used in several new commercial processes, and various design aspects, such as hydrodynamics and mass and heat transfer, have been the subject of investigations in the last few years. However, no attempt to review the scattered information on these novel gas-liquid-solid reactors has been made. Therefore, the main objective of this paper is to review important developments in novel gas-liquid-solid reactors. For each type of reactor, advantages, disadvantages, and applications are discussed. Further, the status of information on hydrodynamics and mass transfer parameters and scale-up considerations is reviewed. These novel reactor designs are being used in several new commercial processes, and various design aspects, such as hydrodynamics and mass and heat transfer, have been the subject of investigations in the last few years. However, no attempt to review the scattered information on these novel gas-liquid-solid reactors has been made. Therefore, the main objective of this paper is to review important developments in novel gas-liquid-solid reactors. For each type of reactor, advantages, disadvantages, and applications are discussed. Further, the status of information on hydrodynamics and mass transfer parameters and scale-up considerations is reviewed.     

合成1,4—丁二醇开发技术中的工艺与工程

合成1,4-丁二醇的大规模工业生产是在国内外同时采用滴流床、浆态床和三相悬浮床三种反应器仅有的反应工艺,对这一反应工艺所用不同反应器的开发方法,包括催化剂制备及考评,各种专用冷模试验和专用反应器的热模试验及动力学测定。应用数学模拟分析和实验相结合,从小试、中试到工业试验,可为大型装置设计提供依据。本文总结了气、液、固三相反应器的基础研究和工业实践相结合的经验、催化剂和反应器工程协调的评价,以及催化剂的制备技术。     

Water treatment using sequenced ozonation and SBR biofilm reactors

The degradation of 3‐methylpyridine (3MEP), a model heterocyclic industrial molecule, was performed in a sequential batch ozonation–biofilm process. Four process steps (bubble‐column ozonation, heterotrophic biofilm degradation, biofilm nitrification, and biofilm denitrification) were combined in different sequences. Three packed‐bed biofilm reactors were started up so as to have separate, specific activities (heterotrophic, nitrification and denitrification). Batch experiments with acetate, ammonia, and nitrate proved that all reactors displayed degradation activity for all substances. Different batch sequences of these reactors were tested with the products of batch ozonation of 3MEP as the first step. The best results were obtained using a two‐step process, in which the ozonation was followed by a single fluidized‐bed, heterotrophic biofilm reactor. The high C/N ratio of 3MEP and the appreciable non‐specific activity of this reactor made it possible to achieve all the biodegradation in the one reactor. Establishing the optimal batch ozonation time (80 min) was determined by an ozone electrode and by stopping the process when the dissolved ozone concentration rose above an initial low level. The identifiable products of 3MEP ozonation were nitrate, acetate, formate, pyruvate, oxalate and ammonium. A C‐balance, compared with TOC measurement, indicated that about 50% of the carbon was in unidentified, but biogradable, ozonation products. Copyright © 2003 Society of Chemical Industry     

Gas-liquid and gas-liquid-liquid reactors with top and bottom blowing: I. Fluid dynamic regimes

The hydrodynamics of G-L and G-L-L0 reactors with top and bottom blowing is investigated. The reactor is a cold model of a 250 ton industrial converter, the different phases present in the real converter (steel-slag-gases) were simulated employing the triphasic system water-vaseline-air; this system was selected to maintain not only the fluidynamic similarity between both reactors. The behaviour of each phase with respect to the other phases employing different top and bottom gas flow rates was analysed. Thus, the formation of gas bubbles in the bulk of the liquid phase (important in the study of G-L mass transfer and in the mixing field), emulsions and drops (important in L-L0 mass transfer) and the streamlines in the reactor were studied to better understand the refining process in the real converter. We also propose flow regime maps with coupling of the different regimes for the three phases present in the reactor, when the gas flow rate is modified.